Process of producing indulin colors.



ADRIANO OSTROGOVICH, OF

area.

TROCESS F PRODUCING ZNDULIN CQLOEW. V

Application filed February a, 1907. 'Serial No. assent.

To all whom it may concern:

Be it known that we, ADRIANO Os'rnooo- VICH, chemist, and TnEoPmLE SILBERMANN, 'diplom engineer, subjects of the King of Roumania, and residing, respectively, at Bucharest, Splaiul General Magheru2, in the Kingdom of Roumania, and at Charlottenburg, Schillerstrasse .120, in the German Empire, have invented new and useful Improve ments in'Processcs for Producing'lndulin and l'ndulin-Like Colors, of which the following is a specification.

Our invention relates to a process for producing indulin and indulinlike colors by heating aromatic amins with halogen withv out addition of acid and has for its object to render the process more expeditious and considerably cheaper, while producing also bettercolors. l 3 i Up to the present, indulins have usually been produced in manufacture by fusing either amidoazocompounds withtaromatic amine and mineral acids or aromatic amins with mineral acids, iron and nitro-compounds, or of anilin with arsenic acid. These methods depend'on oxidizing processes of the kind described by Schultz. The same may be said of the production of indulijn colors by means of chloro-picric-acid (chloro-trinitor-phenol). Besides the above methods employed in manufacture very manyother ways of pro ducing indulins are knownt-thus' Nietzki mentions thatindulins are formed, wherever para-substituted compounds of benzol are.

heated with monoamins in presence of small quantities of mineral acids, provided the neeessary conditions for dehydrating prevail.

We have now found out that indulins may be produced in nearly the theoretical quan- .tity, if aromatic. amins are heated with halo-- gen without any addition of acid. Compounds of anilin and halogen have been already produced often for instance Hoffman prepared iodo-anilin from iodin and anilin, Kckule bromo anilin, azoxy-benzene, etc. from anilin and bromin, Milles several kinds of chloro-anilin from anilin and chlorin. These former experiments did not result in producing indulinlike bodies probably l)0-- cause the savants did not heat the mixture during and after reaction. ployed during the reaction a dirty brownish yellow or brownish red mass is generated containing when cold all kinds of products of the reaction, but not a vestige of indulin. If

' Specification Letters Patent Patented Oct. e, 1908.

this mass is however gradually and very care fully heated again then indulin i formed. If however the mass that has been heated during the reaction and being still warm is raised to a temperature of 180 (1. indulins areforme'd with the greatest ease. The liquid brown substance hardens and turns into a thick krypto-conglomerate of a bronze color, consisting chiefly of indulin and small quantities of amin, which did not enter into the reaction besides halogen-amin and halpgenid of amin. As secondary products azo- )henin and traces of saifranin are formed.

i only azo-phenin is to be produced the temperature must not be raised beyond 120 to ll()'C. "The product of. the reaction is extracted with alcohol leaving the azo-phenin undi'ssolved.

- The following is an example of our process: Equal parts by weight of anilin and iodin are mixed at the usual temperature, the temperature of the mixture gradually. rising of itself to about 70 (3., while its originally brown color changes to ruby. The heating must be continued, the mass becoming thicker at about 100 C. and beginning to crystallize at 140C. On reaching 180, the reaction is at an end. The whole mass is kept for a short time at this temperature and then allowed to cool. When cool it is washed in the usual manner by diluted hydrochloric acid or b adding the. calculated quantity of soda and distilling it with steam.- Nearly the theoretical uantity of indulin is produced. The 'ioilin used passes into the mother lye and can be easily regained therefrom. Iodin and anilin give the bluishviolet indulin colors soluble in alcohol that are known in trade as genuineblue'soluble in alcohol (echt blau spiritliislich) are possible, for instance: Either: anilin is heated under pressure with a quarter of its weight of chlorin to a tem e'rature of 180 (3. or aseous chlorin is conducted into heated 180 by heating the mixture slightly. The chlorin that passes into the anilin is absorbed anilin till the melted mass has attained the desired color and consisten'c The produce is high only chloro-anilin eing formed as secondary product, which does not distil easil with steam. The fused mass is then alka ized with soda and distilled with steam. v

If chlorin is employed several methods ani in'and then the reaction is kept at about entirely, chlorin being conducted into the so lSOlfiriiQ/(l dissolved in glacial c said, the ii-QB'CMEG oi induli'n dissolving n water "Willll :ipore deep blue color. induin arc niso d by heatins hydrochlorid N Bill} or it mixture of the sight of" anilin and l'i di'Q- aniiin to a. coniperiimro of 180 C. and when conducting sir int-o tho incited mass. The same is the case, if rho niixturcs src trcotcd wish load pcroxid or pcrsulfatc or illiilsub-Stan .3. in this case, the oxygen of the air or ol ul'u? oxidizing suhslmico act's no liberate. 1- halogcn according to the following form is, but does not serve to oxidize the onilin, viz

The halogen thus freed rcncbs in slam nasce'nd i upon the aromatic a-niin. The quanxidising substance to he used can he .d. by calculation. 4 i nouicr i'nc-uhod is to pulverizc and mix qnaoiitios by weight of hydrochlorid i rinilin and lcsd pcroxid and then to sprin- Zlurc with a littl'c water or hydrol in order to cause. the reaction to L no icniporsturc oi rho mixture thcn rridually riscs to about 100 (1.. the some ."i'f rhli l'arown. litohcncxiractcd n hm; Wu. for tho purpose of removing rihc chiorid of load. thin. has hecn. formed. The r no is bhcn. heated with hydrochlorid iihri till a tctxopcmiiurc of 180 'rcuchcd. l tcml of using iinlogcns as was first dc- .ad such snhstsinccs nnry ho oiniiloycd port with their illLlilQQOll, for. inwc 4ioir)dwolhyions. it must, he 0:;- ..iy nicntioncd that lvhc noduct-ion of ininims :rz-cordir. i'o our process cannot ho rcgzrrdcd as a process for oxidizing aromatic anin, l'iccrimso rho whole. of tho rcactions P in the sonic inzinncr in n current of car- ,id, "which prccludrs all suhstrniccs r ii oxy r ixhus proving rhzit tho rcl'icuo-i'i docs not (.lc ocnd on on oxidation. Anorlicr proof that chlorin docs not act uni (liriog, ii suhsinnccs giving oli' oxygcn are cxciud cd is found. for instance in. {he fact, that chlorin docs not oxidize benzene to qninon but for mom rcduccs itto licxoi- ChlGi'ulljdi'LFlJcliZimc giving off hydrochloric acid. Nr t :r it mssihlo (O ohrain phic H. 11 hy Lrczmng nuphthulcnc hy chiorrn. as oniy chh "mphihzrlcncs arc l orincd in this uunznor their) inn-y ho oxidixod i' 4 :icid lo phthzilic acid.

n J. rho h or n .L:

ion, than; tho rcaci-ions of out procoss may he dclincd thus: l iinl no atom). of chlorin is added in. thc pnru-posilirm iio the amid and zHiUllHJ atom. of chlorin to the carbon oi tho :nuid. The lruflrcr uloni of chlorin forms hydrochloric acid Willi :rn .nrlom of hydrogen. and lhis cvziporuling allows rhc rest of the molecule to react, with :Luolhcr molecule or ainin thus lUl'Dlillg rho. indulin.

The colors produccd by our process :rrc doubtlcss indulins posscssing in: they do till [he qunlilics of said colors. lhc indulin colonproduced,wiih the :rid of iodin is For redder and than. 'n'oduccd wirh lhc aid ol chlorin for dcopor liluc than tho indulins now on solo. The colorszdl contain a. \Uly snmll quon tit/y of halogcn.

lVlni-t we claim as our invcntlion and dcsirc to sccuro hy lictlcrs if .ilcntv is:

1. A proccss for producing indulin :LlHl indnlin like colors, consisting in heating on aromatic flllllil with ludrjigcn l'o ulmui lhll (1., suhstni'itiolly as dcscrihcd.

2. A n'occss for producing indulin. and indulinlilcc colors, which consists in limiting an aromatic :Mllli'l with :2, snhstirncc which readily yields chlorin in :1 lcinpcrntinr snllicicnt l'o cause said suhslnnco to port with chlorin, substantially as dcscrihcd.

3. A. )roccss for producing indulin and indulinlilro colors, consisting in lrciiling a. fused hydrohuloggcnid of on :u'onurlic :unin Willi an oxidizing suhslzrncc, sulislnnliollv in: dcscrihcd.

4. A. process for producing indulin rind indulinlikc. colors, consisiing in lrcullng ll luscd hydrohologcnid of an nronnilic. :nnnr

with air. suhsinntizrlly us dcscrihml.

5. A procc s for producing indnlin nod induli'nlilw colors, consisting in routing u mixture offuscd aronmli 1: :rniin and :1. hydrohulogcnid of on hlT-Hllzilll, mnin with no oxi dixing snhsL-mcc, substantially as doscrihcd.

6. A nroccss for producing indnlin 11nd indulin liho colors consisling: in lrcuiing n .rnixlurc ol' fuscd m'onmlic :iinins and n hydro hnlogcnid of an zironnitic n-Inin with air. snhstzrnliully as dcscrihod.

in wibncss wl'rcrcof, we suhscrihc our sin nnturcs, in tho nrosonco ol two wilncssm.

ADRIANU ()S'Il-U )GOVKJE I. 'lll. SUJBEHMANN. vl itncssos to signature of ()sirogovich:

"i .iRlNIWIANN, Tnonon nArnnL. l i iincsscs to r'slijlliiilh'r of f-lilhcrnnrnn:

M. Gnomes-inn, A. lietio'rns'nfinn.

lllll 

